Aziridinyl haloformimides

ABSTRACT

Novel carbodiimides of the formula   WHEREIN X is chloro or bromo; R1 and R2 are hydrogen or lower alkyl; and R3 is a hydrocarbyl or a halo- or nitro-substituted hydrocarbyl radical, are disclosed. The carbodiimides are prepared by reacting (a) an aziridine of the formula   WITH (B) AN ISOCYANIDE DIHALIDE OF THE FORMULA R3-N CX2. Novel 1-aziridinecarboximidoyl halides of the formula   D R A W I N G

United States Patent 1 1 Tomalia et al.

[ June 10, 1975 AZIRIDINYL HALOFORMIMIDES [75] Inventors: Donald A. Tomalia; Thomas J.

Giacobbe, both of Midland, Mich.

[73] Assignee: The Dow Chemical Company,

Midland, Mich.

221 Filed: May 11,1973

21 Appl. No.: 359,562

Related U.S. Application Data [62] Division of Ser. No. 76,649, Sept. 29, 1970, Pat. No.

Primary EicaminerAlton D. Rollins Attorney, Agent, or Firm-L. Wayne White [57] ABSTRACT Novel carbodiimides of the formula wherein X is chloro or bromo; R and R are hydrogen or lower alkyl; and R is a hydrocarbyl or a haloor nitro-substituted hydrocarbyl radical, are disclosed The carbodiimides are prepared by reacting (a) an aziridine of the formula with (b) an isocyanide dihalide of the formula R N=CX Novel l-aziridinecarboximidoyl halides of the formula are prepared as intermediates in the process when the process is conducted in the presence of an acid acceptor, e.g. triethylamine. Such intermediates rearrange upon warming, or in the presence of an acid, to form the corresponding carbodiimide.

8 Claims, N0 Drawings 3,888,847 1 2 AZIRIDINYL HALOFORMIMIDES amount of an acid (e.g.. HCl, H 50 HClO H;,PO,,

CF COOH, S AlCl FeCl;,, etc), preferably in the CROSS-REFERENCE TO RELATED APPLICATION presence of an inert solvem This is a division of application Ser. No. 76,649, filed lsocyanide dihalides. as represented y (i) bov are Sept. 29, 1970, now issued as US. Pat. No. 3,754,032. 5 a known Class Of Co pounds. Any compound within this class WllI be suitable for use 1n the sub ect process.

BACKGROUND OF THE INVENTION Representative of such compounds include those in (i) Previous methods of preparing carbodiimides are wherein X is chloro and 3 is y hy yl, cysummarized in Chemical Reviews, 67, 107-52 by F. OheXyl, octyl, dodecyl, octadecyl, phenyl, naphthyl, Kurzer et al. The reference also contains a general sumof py m y p yl. y ph yl. mary of the known carbodiimides and their general 4-octylphenyl, benzyl, phenethyl, B-naphthylethyl, 4- utilities, phenylbutyl, 4-aminophenyl, 3-aminophenyl, 2-

fluorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 4-

SUMMARY OF THE INVENTION iodophenyl, and the like, and the corresponding com- It has now been discovered that novel asymmetric, pounds wherein X is bromo. The preferred isocyanide 2-chloroalkyl carbodiimides of the general formula dihalide reactants are those in (i) wherein X is chloro, and most preferred are those wherein X is chloro and -31 R is aryl or haloor nitro-substituted aryl.

, Suitable aziridine reactants, (ii), include aziridine Y-C- "i "--L=L I I 3 (ethylenimine), 2-methylaz1ridme, 2,2-

' dimeth laziridine, Z-ethylaziridine, 2-butylaziridine, y

and the like. Preferably, (11) is aziridine, 2- Wherein X is chloro or bmmoz R1 and R2 are hydrogen methylaziridine or 2,2-dimethylaziridine, and most or lower alkyl; and R is alkyl, cycloalkyl, aryl, alkaryl, Preferably i is aziridine" aralkyl or haloor nitro-substituted aryl, are conve- The reactlon timperatuore gene ral ly selected niently prepared in the novel reaction comprising retween about 20 and If the mdlrect process 15 acting by contacting (a) an aziridine of the formula followed, the temperature is f f' p y maintained tween about 20 and 5C. until (1v) is formed. At temperatures above about 50C., the product yield in some R1 30 instances is lowered due to the formation of polymeric y pro ucts.

The stoichiometry of the reaction requires 1 mole of R and R having the above meaning, with (b) an isocy- (i) per mole of (ii). However, an excess of either (i) or anide dihalide of the formula R -N CX X and R (ii) may be used, e.g. from 1 to 3 times the stoichiomethaving the above meaning. The subject carbodiimides ric amount, or-more. In the indirect process, at least 1 are useful, for example, as monomers, polymerization mole of acid acceptor is preferably included per mole promoters and as stabilizers for polymers which are of HX generated; if less than 1 mole of acid acceptor subject to degradation due to heat, light and/or hydroper mole of I-IX is used, the product yield of (iv) may lysis. be lowered due to formation of (iii) and/or polymeric The novel process is represented by equations (1) 4O by-products. and/or (II). Pressure on the reaction is not critical. Atmospheric l 2, 31 i tr) 3 -542 i a-az-em' i. i am e R x I l .gacz 3am l & 3 heat a) 3 aceep H 3 or (iii) acid The direct process represented by (I) is generally an pressure is convenient and generally used. exothermic reaction. The product yields from (I) may The process, whether via equation (I) or (II), is prefbe lowered due to formation of polymeric by-products. erably conducted in an inert solvent, such as carbon The indirect process, (II), proceeds smoothly in the tetrachloride, methyl chloroform, chloroform, bromopresence of an acid acceptor, e.g. triethylamine or pyriform, benzene, toluene, hexane, etc. Carbon tetrachlodine, to form an intermediate, (iv), and a hydrohalide ride is preferred in most instances. salt. The intermediate, (iv), is then easily isomerized to Th subject carbodiimides, are g n lly iq i form the desired product by merely (a) warming same which may be used in substantially the same manner as to a temperature sufficient to cause ring opening of the were other carbodiimides (see Kurzer et al. above) to achieve similar results. Additionally, the subject car- 3 bodiimides can be homopolymerized to give unique 3 I polymers bearing reactive chloroalkyl groups which are themselves useful, as chelating agents, for example, or

which can be further reacted with ammonia or other group, preferably in the presence of an inert solvent, or amines to g quaternary ammoniumbearing P y- (b) forming an admixture of (iv) and a catalytic mers which are useful, for example, as ion exchange resins. Additionally, the subject carbodiimides may be copolymerized with other known carbodiimides to form polymers which are similarly useful. Such polymerizatlon reactions occur upon heating the mono- A sample (0.3 g.) of lA was warmed in a vessel equipped with a condenser and drying tube at a temperature of 68C. for 12 minutes. The resulting yellow liquid, l-B, was produced in quantitative yield from y a m ng the m0fl0mer($) in the Presence 5 l-A and in from 88100 percent yield in a series of of a Sultable Catalyst See, for examplfi, Pat runs, based on starting materials. Elemental analysis 3,200,087 which describes certain carbodiimide polyh d; lqlerrs an po ymerlzatlon catalysts which may be used Theory Found SPECIFIC EMBODIMENTS Z. 5 5.25 Is The following examples further illustrate the inventi In a subsequent experiment, a sample of 1-A was dissolved in acetone containing a catalytic amount of hy- EXAMPLE 1 drochloric or perchloric acid. The conversion of l-A Preparation of to 1B proceeded smoothly to completion in 1 hour at N-( 2-chloroethyl )-N -m-nitrophenylcarbodiimide room temperature.

Cl aato -c a -xdzci ar-a I mciae no can; 5 a

0'-5C. lz.

A solution of aziridine (0.1 mole) and triethylamine (0.1 mole) in 75 ml. of carbon tetrachloride was added dropwise to a stirred, pre-cooled solution of mnitrophenyl isocyanide dichloride (0.1 mole) in 75 ml.

of carbon tetrachloride over a period of 1.5 hours; the temperature was maintained between 0 and 5C. during this time. The reaction mixture was warmed to room temperature and maintained at room temperature for 0.5 hour with continued stirring. Triethylamine hydrochloride was removed from the reaction mixture by filtration and the solvent and other volatiles were removed from the filtrate under reduced pressure. Compound l-A was thus obtained as a crystalline solid which, after recrystallization from diethyl ether, had a melting point of 6870C. The compound was stable at 5 to 0C. for several months. Elemental analysis showed:

Theory Found EXAMPLES 2-6 In like manner, the following carbodiimides were prepared in accordance with the equation o it The products, n-B, were typically obtained by warming a solution of n-A in CCL, at 40C. until the isomerization was complete, e.g. 14 hours and 31 hours for Examples 2 and 3, respectively. Alternatively, n-B was formed by stirring n-A in an acetone/hydrochloric or perchloric acid solution for 1 hour at room temperature. In both procedures, the product, n-B, was formed in essentially quantitative yield, based on n-A, and in 80-100 percent yield, based on starting materials.

In some instances, n-B was formed by merely warming n-A neat, e.g. Examples 2 and 6. Pursuant to this procedure, however, Example 6-A yielded a mixture of 6-B and What is claimed is: l. A compound of the formula 3. The compound of claim 1 wherein X is chloro.

4. The compound of claim 1 wherein R is phenyl, naphthyl, monoor dihalosubstituted phenyl or mononitrosubstituted phenyl.

5. The compound of claim 4 wherein R is phenyl or naphthyl.

6. The compound of claim 5 wherein R is phenyl.

7. The compound of claim 1 wherein R and R are H, X is chloro and R is phenyl.

8. A process for producing the compound defined in claim 1 comprising reacting by contacting, in the presence of an acid acceptor, (a) an aziridine of the formula with (b) an isocyanide dihalide of the formula 'R N CX said process being conducted at a temperature of from about 20 to about 5C. 

1. A COMPOUND OF THE FORMULA
 2. The compound of claim 1 wherein R1 and R2 are H or CH3.
 3. The compound of claim 1 wherein X is chloro.
 4. The compound of claim 1 wherein R3 is phenyl, naphthyl, mono-or dihalosubstituted phenyl or mononitrosubstituted phenyl.
 5. The compound of claim 4 wherein R3 is phenyl or naphthyl.
 6. The compound of claim 5 wherein R3 is phenyl.
 7. The compound of claim 1 wherein R1 and R2 are H, X is chloro and R3 is phenyl.
 8. A PROCESS FOR PRODUCING THE COMPOUND DEFINED IN CLAIM 1 COMPRISING REACTING BY CONTACTING, IN THE PRESENCE OF AN ACID ACCEPTOR, (A) AN AZIRIDINE OF THE FORMULA 